WO2004000798A1 - N-sulphonylaminoacetonitriles having pesticidal properties - Google Patents

N-sulphonylaminoacetonitriles having pesticidal properties Download PDF

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Publication number
WO2004000798A1
WO2004000798A1 PCT/EP2003/006483 EP0306483W WO2004000798A1 WO 2004000798 A1 WO2004000798 A1 WO 2004000798A1 EP 0306483 W EP0306483 W EP 0306483W WO 2004000798 A1 WO2004000798 A1 WO 2004000798A1
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Prior art keywords
alkyl
halo
formula
compound
alkoxy
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PCT/EP2003/006483
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French (fr)
Inventor
Arthur Steiger
Werner Zambach
Jacques Bouvier
Pierre Ducray
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Novartis Ag
Novartis Pharma Gmbh
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Filing date
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Application filed by Novartis Ag, Novartis Pharma Gmbh filed Critical Novartis Ag
Priority to BR0311967-0A priority Critical patent/BR0311967A/en
Priority to AU2003242735A priority patent/AU2003242735B8/en
Priority to EP03760656A priority patent/EP1517887A1/en
Priority to US10/518,063 priority patent/US20050222448A1/en
Priority to KR10-2004-7020580A priority patent/KR20050014011A/en
Priority to CA002490123A priority patent/CA2490123A1/en
Priority to MXPA04012755A priority patent/MXPA04012755A/en
Priority to JP2004514794A priority patent/JP2005529967A/en
Priority to NZ537039A priority patent/NZ537039A/en
Publication of WO2004000798A1 publication Critical patent/WO2004000798A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/275—Nitriles; Isonitriles
    • A61K31/277—Nitriles; Isonitriles having a ring, e.g. verapamil
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/12—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
    • C07C311/13—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings the carbon skeleton containing six-membered aromatic rings

Definitions

  • Some compounds of formula (I) may be in the form of tautomers.
  • the compounds of formula (I) are therefore to be understood hereinbefore and hereinafter as including corresponding tautomers, where appropriate, even if the latter are not specifically mentioned in each case.
  • R 2 is C ⁇ -C 6 alkyl, halo-C ⁇ -C 6 alkyl, aryl or heteroaryl which is in each case unsubstituted or mono- to polysubstituted by R 7 , where the substituents can in each case be identical or different if their number is greater than 1 ; particularly CrC 6 alkyl, halo-CrC 6 alkyl or aryl which is unsubstituted or mono- to pentasubstituted by R 7 , where the substituents can be identical or different if their number is greater than 1 ; very particularly aryl which is unsubstituted or mono- to trisubstituted by R 7 , where the substituents can be identical or different if their number is greater than 1 ;
  • solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydr
  • the said animal pests of plants include those mentioned in European Patent Application EP-A-736252, page 5, line 55 to page 6, line 55.
  • the pests mentioned therein are therefore included by reference in the subject matter of the present invention.
  • the compounds of formula (I) can also be used against pests affecting hygiene, especially of the order Diptera with the families Sarcophagidae, Anophilidae and Culicidae; and of the orders Orthoptera, Dictyoptera (e.g. the family Blattidae) and Hymenoptera (e.g. the family Formicidae).
  • ectoparasites occurring as parasites on warmblooded organisms are understood to mean especially insects, mites and ticks. Included are insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysan- optera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.
  • ticks are, for example, Boophilus, Ambly- omma, Anocentor, Dermacentor, Haemaphysalis, Hyalomma, Ixodes, Rhipicentor, Margar- alphabet, Rhipicephalus, Argas, Otobius and Ornithodoros and the like, which preferentially infest warm-blooded animals, including farm animals, such as cows, pigs, sheep and goats, poultry, such as hens, turkeys and geese, animals bred for their fur, such as mink, fox, chinchillas, rabbits and the like, and domestic animals, such as cats and dogs, but also humans.
  • farm animals such as cows, pigs, sheep and goats
  • poultry such as hens, turkeys and geese
  • animals bred for their fur such as mink, fox, chinchillas, rabbits and the like
  • domestic animals such as cats and dogs, but also humans.
  • the compounds of formula (I) are suitable for controlling parasites that are pathogens of humans, among which, as typical representatives occurring in the digestive tract, mention should be made of those of the species Ancylostoma, Necator, Ascaris, Strongyloides, Trichinella, Capillaria, Trichuris and Enterobius.
  • the compounds of the present invention are also effective against parasites of the species Wuchereria, Brugia, Onchocerca and Loa from the family of the Filariidae, which occur in the blood, in tissue and various organs, and also against Dracunculus and parasites of the species Strongyloides and Trichinella, which infect especially the gastrointestinal tract.
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • compositions according to the invention are also suitable for protecting plant propagation material, including genetically modified propagation material, e.g. seed material, such as fruit, tubers or grains, or plant cuttings, from animal pests.
  • the propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown.
  • the compounds according to the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation.
  • the formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.

Abstract

The invention relates to compounds of the general formula (I) and, if appropriate, enantiomers thereof. The active compounds have advantageous pesticidal properties. They are suitable, in particular, for the control of parasites in warm-blooded animals.

Description

N-Sulphonylaminoacetonitriles having pesticidal properties
The present invention relates to novel sulphonylaminoacetonitrile compounds of the formula
Figure imgf000002_0001
in which
Ri is aryl or heteroaryl, in each case unsubstituted or mono- or polysubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ;
R2 is CrCealkyl, halo-C Cealkyl, C3-C8cycloalkyl, halo-C3-C8cycloalkyl, NHR8; aryl or heteroaryl, in each case unsubstituted or mono- or polysubstituted by R , where the substituents can in each case be identical or different if their number is greater than 1 , or pyrrolidinyl, piperidinyl, imidazolidinyl, piperazinyl, pyrazolidinyl, morpholinyl, indolinyl or isoindolinyl, in each case bonded via N;
R3 is hydrogen, C C6alkyl, halo-CrC6alkyl, CrCβalkoxy-CrCealkyl, benzyl, CrC6alkyl- heteroaryl, CrC6alkoxycarbonyl or Cι-C6alkylcarbonyl;
R , R5 and R6 either independently of one another are hydrogen, halogen, CrC6alkyl, halo- C C6alkyl, CrC6alkoxy, halo-C C6alkoxy, C C6alkylthio, halo-d-C-ealkylthio, C2-C6alkenyl, C2-C6alkynyl, unsubstituted or substituted C3-C8cycloalkyl, where the substituents are selected from the group consisting of halogen and Cι-C6alkyl, or unsubstituted or substituted phenyl, where the substituents are selected from the group consisting of halogen, CrCealkyl and phenyl; or R4 and R5, together with the carbon atoms to which they are bonded, are a five- to seven- membered, saturated or partially unsaturated heterocyclic ring having 1 or 2 heteroatoms from the group consisting of nitrogen, oxygen and sulphur;
R7 is halogen, C C6alkyl, halo-Cι-C6alkyl, CrC6alkoxy, halo-C C6alkoxy, d-Cealkylthio, halo-Cι-C6alkylthio, C2-C6alkenyl, C2-C6alkynyl; aryl, phenylacetylenyl or heteroaryl, in each case unsubstituted or mono- or polysubstituted, where the substituents are in each case selected from the group consisting of halogen, nitro, cyano, CrC6alkyl, halo-CrC6alkyl, CrC6alkoxy, halo-C C6alkoxy, and can in each case be identical or different if their number is greater than 1 ; R8 is aryl which is unsubstituted or mono- to pentasubstituted, where the substituents are selected from the group consisting of halogen, nitro, cyano, CrC6alkyl, halo-Cr C6alkyl, CrC6alkoxy and halo-Cι-C6alkoxy, and can be identical or different if their number is greater than 1 ;
X is O, S, S(O) or S(O)2; and n is 0 or 1 ; and, if appropriate, E/Z isomers, E/Z isomer mixtures and/or tautomers, in each case in free form or in salt form; a process for preparation and the use of these compounds, their isomers and tautomers; starting compounds for the preparation of the compounds of the formula (I); pesticides whose active compound is selected from the compounds of the formula (I) and their tautomers; and a process for the control of plant-injurious insects and representatives of the order Acarina, and of endo- and ectoparasites, in particular helminths, in and on warm-blooded agricultural and domestic animals, using these compositions.
Substituted aminoacetonitrile compounds having pesticidal action are described in the literature. The active compounds actually disclosed there however, cannot always fulfil the requirements with respect to potency and spectrum of action. There is thus a need for active compounds having improved pesticidal properties. It has now been found that the compounds of the formula (I) according to the invention have outstanding pesticidal properties, in particular against endo- and ectoparasites in and on agricultural and domestic animals and plants.
Some compounds of formula (I) may be in the form of tautomers. The compounds of formula (I) are therefore to be understood hereinbefore and hereinafter as including corresponding tautomers, where appropriate, even if the latter are not specifically mentioned in each case.
The compounds of formula (I) and, where appropriate, tautomers thereof are capable of forming salts, for example acid addition salts. Those acid addition salts are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, e.g. halo-substituted, Cι-C4alkanecarboxylic acids, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric and phthalic acid, hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric and citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, e.g. halo-substituted, Cι-C alkane- or aryl-sulfonic acids, e.g. methane- or p-toluene-sulfonic acid. Furthermore, compounds of formula (I) having at least one acid group are capable of forming salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal and alkaline earth metal salts, e.g. sodium, potassium and magnesium salts, and salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri- lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri- hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. In addition, corresponding internal salts may optionally also be formed. Preference is given, firstly, to the free form. Among the salts of compounds of formula (I) preference is given to agrochemically advantageous salts. The free compounds of formula (I) and salts thereof are to be understood hereinbefore and hereinafter as including, where appropriate, both the corresponding salts and the free compounds of formula (I), respectively. The same is correspondingly true for tautomers of compounds of formula (I) and salts thereof.
The general terms used hereinbefore and hereinafter have the following meanings, unless defined otherwise.
Aryl is phenyl or naphthyl.
Heteroaryl is pyridyl, pyrimidyl, s-triazinyl, 1 ,2,4-triazinyl, thienyl, furanyl, pyrryl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, benzofuranyl, benzothiazolyl, indolyl or indazolyl, preferably pyridyl, pyrimidyl, s-triazinyl or1 ,2,4-triazinyl, in particular pyridyl or pyrimidyl.
Alkyl - as a group per se and as a structural element of other groups and compounds, such as of haloalkyl.alkoxy and alkylthio, - is, in each case taking into account the number of the carbon atoms included from case to case in the corresponding group or compound, either straight-chain, that is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Alkenyl - as a group per se and as a structural element of other groups and compounds - is, in each case taking into account the number of the carbon atoms and conjugated or isolated double bonds included from case to case in the corresponding group or compound, either straight-chain, e.g. allyl, 2-butenyI, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1 ,3-hexadienyl or 1 ,3-octadienyl, or branched, e.g. isopropenyl, isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, isoheptenyl or isooctenyl. Alkynyl - as a group per se and as a structural element of other groups and compounds - is, in each case taking into account the number of the carbon atoms and conjugated or isolated double bonds included from case to case in the corresponding group or compound, either straight-chain, e.g. propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl, or 1 ,5-heptadien-3-ynyl, or branched, e.g.3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex- 2-ynyl or 2-methylhept-3-ynyl.
Cycloalkyl - as a group per se and as a structural element of other groups and compounds, such as of halocycloalkyl - is, in each case taking into account the number of the carbon atoms included from case to case in the corresponding group or compound, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Halogen - as a group per se and as a structural element of other groups and compounds - such as of haloalkyl, haloalkoxy and haloalkylthio - is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine.
Halogen-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkoxy or haloalkylthio, can be partially halogenated or perhalogenated, it being possible in the case of polysubstitution for the halogen substituents to be identical or different. Examples of haloalkyl - as a group per se and as a structural element of other groups and compounds - such as of haloalkoxy, or haloalkylthio, are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF2 or CF3; ethyl which is mono- to penta- substituted by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCI3, CF2CHCI2, CF2CHF2, CF2CFCI2, CF2CHBr2, CF2CHCIF, OH2CHBrF or CCIFCHCIF; propyl or isopropyl which is one mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; butyl or one of its isomers which is mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF3)CHFCF3 or CH2(CF2)2CF3; pentyl or one of its isomers which is mono- to undecasubstituted by fluorine, chlorine and/or bromine, such as CF(CF3)(CHF)2CF3 or CH2(CF2)CF3; and hexyl or one of its isomers which is mono- to tridecasubstituted by fluorine, chlorine and/or bromine, such as (CH2)4CHBrCH2Br, CF2(CHF)4CF3, CH2(CF2)4CF3 or C(CF3)2(CHF)2CF3.
Alkoxy groups preferably have a chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy, and the isomers pentyloxy and hexyloxy; preferably methoxy and ethoxy. Haloalkoxy groups preferably have a chain length of 1 to 6 carbon atoms. Haloalkoxy is, for example, fluoro- methoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoro-ethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
Alkylthio groups preferably have a chain length of 1 to 6 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio.
Preferred embodiments within the context of the invention, taking into account the above- mentioned proviso, are:
(1) a compound of the formula (I), in which Ri is aryl which is unsubstituted or mono- to pentasubstituted by R7, where the substitutents in each case can be identical or different if their number is greater than 1 ; particularly aryl which is mono- to trisubstituted by R , where the substituents in each case can be identical or different if their number is greater than 1 ;
(2) a compound of the formula (I), in which R2 is Cι-C6alkyl, halo-Cι-C6alkyl, aryl or heteroaryl which is in each case unsubstituted or mono- to polysubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ; particularly CrC6alkyl, halo-CrC6alkyl or aryl which is unsubstituted or mono- to pentasubstituted by R7, where the substituents can be identical or different if their number is greater than 1 ; very particularly aryl which is unsubstituted or mono- to trisubstituted by R7, where the substituents can be identical or different if their number is greater than 1 ;
(3) a compound of the formula (I), in which R3 is hydrogen or Ci-Cβalkyl; particularly hydrogen or Cι-C4alkyl; very particularly hydrogen;
(4) a compound of the formula (I), in which R4, R5 and R6 independently of one another are hydrogen, CrC6alkyl, halo-Cι-C6alkyl, Cι-C6alkoxy, halo-Cι-C6alkoxy, C2-C6alkenyl, C2-C6- alkynyl, C3-C6cycloalkyl; particularly hydrogen, Cι-C4alkyl, halo-Cι-C alkyl or C3-C6cycloalkyl; very particularly hydrogen or CrC2alkyl.
(5) a compound of the formula (I), in which R7 is halogen, d-C4alkyl, halo-d-C alkyl, d-C4- alkoxy, halo-d-C4alkoxy; aryl or phenylacetylenyl, in each case unsubstituted or mono- or polysubstituted, where the substituents are selected from the group consisting of halogen, Cι-C6alkyl, halo-d-C6alkyl, d-C6alkoxy, halo-d-Cβalkoxy, and can in each case be identical or different if their number is greater than 1 ; particularly halogen, CrCaalkyl, halo-d-C2alkyl, Cι-C2alkoxy, halo-d-C2alkoxy; very particularly halogen or halo-d-C2alkyl;
(6) a compound of the formula (I), in which R8 is unsubstituted or mono- to trisubstituted aryl, where the substituents are selected from the group consisting of halogen, d-C4alkyl, halo- d-dalkyl, C1-C alkoxy and halo-Cι-C4alkoxy, and can be identical or different if their number is greater than 1 ; particularly mono- to trisubstituted aryl, where the substituents are selected from the group consisting of halogen, d-C2alkyl, halo-d-C2alkyl, and halo-d- C2alkoxy, and can be identical or different if their number is greater than 1 ; very particularly mono- or disubstituted aryl, where the substituents are selected from the group consisting of halogen and halo-d-C2alkyl, and can be identical or different if their number is greater than 1;
(7) a compound of the formula (I), in which X is O or S; particularly O;
(8) a compound of the formula (I), in which n is 1 ;
(9) a compound of the formula (I), in which ^ is aryl which is unsubstituted or mono- or pentasubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ; R2 is d-C6alkyl, halo-d-C6alkyl, aryl or heteroaryl, in each case unsubstituted or mono- or polysubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ; R3 is hydrogen or d-C6alkyl; R4, R5 and R6 independently of one another are hydrogen, d-C6alkyl, halo-C C6alkyl, d-C6alkoxy, halo-d-C6alkoxy, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl; R7 is halogen, d-C4alkyl, halo-d-C4alkyl, d-C4alkoxy, halo-d-C4alkoxy, aryl or phenylacetylenyl, in each case unsubstituted or mono- or polysubstituted, where the substituents are selected from the group consisting of halogen, d-C6alkyl, halo-CrC6alkyl, d-C6alkoxy, halo-d-C6alkoxy, and in each case can be identical or different if their number is greater than 1 ; R8 is unsubstituted or mono- to trisubstituted aryl, where the substituents are selected from the group consisting of halogen, d-C4alkyl, halo-C C4alkyl, CrC alkoxy and halo-d-C4alkoxy, and can be identical or different if their number is greater than 1 ; X is O or S; and n is 1 ;
(10) a compound of the formula (I), in which R^ is aryl which is mono- or trisubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1; R2 is d-C6alkyl, halo-d-C6alkyl or aryl which is unsubstituted or mono- to pentasubstituted by R7, where the substituents can be identical or different if their number is greater than 1 ; R3 is hydrogen or Cι-C4alkyl; R4, R5and R6 independently of one another are hydrogen, d-C4alkyl, halo-d-C4alkyl or C3-C6cycloalkyl; R7 is halogen, d-C2alkyl, halo- d-C2alkyl, C C2alkoxy or halo-d-C2alkoxy; R8 is mono- to trisubstituted aryl, where the substituents are selected from the group consisting of halogen, d-C2alkyl, halo-d-C2alkyl, and halo-d-Qjalkoxy, and can be identical or different if their number is greater than 1 ; X is O; and n is 1 ; (11) a compound of the formula (I), in which Ri is aryl which is mono- to trisubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1; R2 is aryl which is unsubstituted or mono- to trisubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ; R3 is hydrogen; R4, R5 and R6 independently of one another are hydrogen or d-C2alkyl; R7 is halogen or halo-d-C2alkyl; R8 is mono- or disubstituted aryl, where the substituents are selected from the group consisting of halogen and halo-d-C2alkyl, and can be identical or different if their number is greater than 1 ; X is O; and n is 1.
Particularly preferred compounds of the formula (I) for the purposes of the invention are those listed in tables 1 and 2 and very particularly preferably the compounds of the formula (I) mentioned in the synthesis examples.
A further subject of the invention is the process for the preparation of the compounds of the formula (I), in each case in free form or in salt form, characterized in that a compound of the formula
Figure imgf000008_0001
which is known or can be prepared in analogy to corresponding known compounds and in which Ri, R3| R4, R5, R6, X and n are as defined for the formula (I), is reacted with a compound of the formula
Figure imgf000008_0002
which is known or can be prepared in analogy to corresponding known compounds and in which R2 is as defined for the formula (I) and Q is a leaving group, if appropriate in the presence of a basic catalyst, and in each case, if desired, a compound of the formula (I), in each case in free form or in salt form, obtainable according to the process or in another manner, is converted into another compound of the formula (I), a mixture of isomers obtainable according to the process is separated and the desired isomer is isolated and/or a free compound of the formula (I) obtainable according to the process is converted into a salt or a salt of a compound of the formula (I) obtainable according to the process is converted into the free compound of the formula (I) or into another salt. For starting materials mentioned above and below, it applies with respect to their salts that what has been said above for salts of compounds of the formula (I) applies in an analogous manner.
The reactants can be reacted with one another as such, that is without addition of a solvent or diluent, e.g. in the melt. Usually, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; amides, such as N.N-dimethylformamide, N,N-diethyl- formamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoramide; nitriles, such as acetonitrile or propionitrile; and sulphoxides, such as dimethyl sulphoxide.
Preferred leaving groups are halogens, in particular chlorine.
Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkoxides, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated, unsaturated or saturated, cycloalkylamines, basic heterocycles, ammonium hydroxides, and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, hydride, amide, methoxide, acetate, carbonate, potassium t-butoxide, hydroxide, carbonate, hydride, lithium diisopropyl- amide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropyla ine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N.N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethyl- ammonium hydroxide, and 1 ,5-diazabicyclo[5.4.0]undec-5-ene (DBU).
The reaction is advantageously carried out in a temperature range from approximately 0°C to approximately + 150°C, preferably from approximately 20°C to approximately + 100°C.
A further subject of the invention is the process for the preparation of the compounds of the formula (II), in each case in free form or in salt form, for example characterized in that a compound of the formula
Figure imgf000010_0001
which is known or can be prepared in analogy to corresponding known compounds and in which Ri, R4, R5, R6, X and n are as defined for the formula (I), is reacted with an inorganic or organic cyanide and a compound of the formula R3-NH2, which is known or can be prepared in analogy to corresponding known compounds and in which R3 is as defined for the formula (I), and in each case, if desired, a compound of the formula (II), in each case in free form or in salt form, obtainable according to the invention or in another manner, is converted into another compound of the formula (II), a mixture of isomers obtainable according to the process is separated and the desired isomer is isolated and/or a free compound of the formula (II) obtainable according to the process is converted into a salt or a salt of a compound of the formula (II) obtainable according to the process is converted into the free compound of the formula (II) or into another salt.
Suitable cyanides are sodium cyanide, potassium cyanide, trimethylsilyl cyanide and acetone cyanohydrin.
Compounds of formula (I) obtainable in accordance with the process or by another method can be converted in a manner known perse into different compounds of formula (I) by replacing one or more substituents of the starting compound of formula (I) by (an)other substituents) according to the invention in customary manner.
Depending upon the reaction conditions and starting materials selected as suitable in each case, it is possible in a reaction step to replace only one substituent by another substituent according to the invention or it is possible in the same reaction step to replace a plurality of substituents by other substituents according to the invention.
Salts of compounds of formula (I) can be prepared in a manner known perse. For example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.
Salts of compounds of formula (I) can be converted in customary manner into the free compounds of formula (I); acid addition salts can be converted, for example, by treatment with a suitable basic medium or a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent. Salts of compounds of formula (I) can be converted into different salts of compounds of formula (I) in a manner known perse; for example acid addition salts can be converted into different acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt being formed, for example silver chloride, is insoluble and is therefore precipitated out from the reaction mixture.
Depending upon the procedure and/or the reaction conditions, the compounds of formula (I) having salt-forming properties can be obtained in free form or in the form of salts.
The compounds of formula (I) can also be obtained in the form of their hydrates and/or can include other solvents, for example any solvent that may have been used for the crystallisation of compounds in solid form.
The compounds of formulae (I) and (II) may be in the form of one of the possible isomers or in the form of a mixture thereof, for example depending upon the number of asymmetric carbon atoms and the absolute and relative configuration thereof, in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood accordingly hereinbefore and hereinafter, even when stereochemical details are not specifically mentioned in each case.
Mixtures of diastereoisomers and mixtures of racemates of compounds of formulae (I) and (II) obtainable in accordance with the process - depending upon the starting materials and procedures chosen - or by other means can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physico-chemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.
Mixtures of enantiomers or racemates so obtainable can be separated into the optical antipodes by known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific immobilised enzymes, or via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed. Pure diastereoisomers and enantiomers can be obtained not only by separation of corresponding mixtures of isomers but also, according to the invention, by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials that have appropriate stereochemistry.
It is advantageous to isolate or synthesise whichever isomer, for example enantiomer, or mixture of isomers, for example mixture of enantiomers, is biologically more active, insofar as the individual components have different biological activity.
In the process of the present invention there are preferably used those starting materials and intermediates which result in the compounds of formula (I) described at the beginning as being especially valuable.
The invention relates especially to the preparation process described in the Example.
The invention relates also to the novel starting materials and intermediates that are used according to the invention in the preparation of compounds of formula (I), to their use and to processes for the preparation thereof.
In the area of pest control, the compounds of formula (I) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum, even at low rates of concentration, while being well tolerated by warmblooded organisms, fish and plants. The compounds are especially suitable for use in the area of controlling endo- and ecto-parasites of animals and plant-destructive insects and representatives of the order Acarina. The active ingredients according to the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina. The pesticidal activity of the active ingredients according to the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %. The compounds of formula (I) are especially distinguished by an unusually long duration of action.
The said animal pests of plants include those mentioned in European Patent Application EP-A-736252, page 5, line 55 to page 6, line 55. The pests mentioned therein are therefore included by reference in the subject matter of the present invention. The compounds of formula (I) can also be used against pests affecting hygiene, especially of the order Diptera with the families Sarcophagidae, Anophilidae and Culicidae; and of the orders Orthoptera, Dictyoptera (e.g. the family Blattidae) and Hymenoptera (e.g. the family Formicidae).
The compounds of formula (I) also have long-lasting activity in the case of mites and insects that are parasites of plants. In the case of spider mites of the order Acarina, they are effective against eggs, nymphs and adults of Tetranychidae (Tetranychus spp. and Panonychus spp.).
They possess a high degree of activity in sucking insects of the order Homoptera, especially against pests of the families Aphididae, Delphacidae, Cicadellidae, Psyllidae, Loccidae, Diaspididae and Eriophydidae (e.g. rust mite on citrus fruit); of the orders Hemiptera, Heter- optera and Thysanoptera, and in phytophagous insects of the orders Lepidoptera, Cole- optera, Diptera and Orthoptera.
They are also suitable as a soil insecticide against pests in the soil.
The compounds according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases parts of plants that grow later are still protected against those pests.
The compounds of formula (I) are therefore effective against all development stages of sucking and phytophagous insects on crops such as cereals, e.g. wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g. strawberries, raspberries and blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals. The compounds of formula (I) are also effective against plant-nematodes of the species Meloidogyne, Heterodera, Pratylenchus, Ditylenchus, Radopholus, Rizoglyphus and others.
In the context of the present invention, ectoparasites occurring as parasites on warmblooded organisms are understood to mean especially insects, mites and ticks. Included are insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysan- optera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera. Special mention may be made, however, of ectoparasites that trouble humans and animals and transmit pathogens, for example flies, such as Musca domestica, Musca vetustissima, Musca autumnalis, Fannia canicularis, Sarcophaga carnaria, Lucilia cuprina, Hypoderma bovis, Hypoderma lineatum, Chrysomyia chloropyga, Dermatobia hominis, Cochliomyia hominivorax, Gasterophilus intestinalis, Oestrus ovis, Stomoxys calcitrans, Haematobia irritans and midges (Nematocera), such as Culicidae, Simuliidae, Psychodidae, and also bloodsucking parasites, for example fleas, such as Ctenocephalides felis and Ctenocephalides canis (cat and dog fleas), Xenopsylla cheopis, Pulex irritans, Dermatophilus penetrans, lice, such as Damalina ovis, Pediculus humanis, stable flies and horse flies (Tabanidae), Haematopota spp., such as Haematopota pluvialis, Tabanidea spp., such as Tabanus nigrovittatus, Chrysopsinae spp., such as Chrysops caecutiens, tsetse flies, such as Glossinia species, biting insects, especially cockroaches, such as Blatella germanica, Blatta orientalis, Periplaneta americana, mites, such as Dermanyssus gallinae, Sarcoptes scabiei, Psoroptes ovis and Psorergates spp. and, not least, ticks. The latter belong to the order Acarina. Known examples of ticks are, for example, Boophilus, Ambly- omma, Anocentor, Dermacentor, Haemaphysalis, Hyalomma, Ixodes, Rhipicentor, Margar- opus, Rhipicephalus, Argas, Otobius and Ornithodoros and the like, which preferentially infest warm-blooded animals, including farm animals, such as cows, pigs, sheep and goats, poultry, such as hens, turkeys and geese, animals bred for their fur, such as mink, fox, chinchillas, rabbits and the like, and domestic animals, such as cats and dogs, but also humans.
In addition, the compounds of formula (I) are especially effective against helminths, among which the endoparasitic nematodes and trematodes may be the cause of serious diseases of mammals and poultry, for example of sheep, pigs, goats, cattle, horses, donkeys, dogs, cats, guinea-pigs and ornamental birds. Typical nematodes in that indication are: Haem- onchus, Trichostrongylus, Ostertagia, Nematodirus, Cooperia, Ascaris, Bunostonum, Oeso- phagostonum, Chabertia, Trichuris, Strongylus, Trichonema, Dictyocaulus, Capillaria, Heterakis, Toxocara, Ascaridia, Oxyuris, Ancylostoma, Uncinaria, Toxascaris and Para- scaris. Among the trematodes special mention should be made of the family of the Fascio- lideae, especially Fasciola hepatica. The special advantage of the compounds of formula (I) is their efficacy against such parasites that are resistant to benzimidazole-based active ingredients.
Certain Nematodirus, Cooperia and Oesophagostonum species attack the intestinal tract of the host animal whereas others of the species Haemonchus and Ostertagia parasitise in the stomach and those of the species Dictyocaulus parasitise in pulmonary tissue. Parasites of the families Filariidae and Setariidae are found in the internal cell tissue and the organs, for example the heart, the blood vessels, the lymph vessels and the subcutaneous tissue. In this context special mention should be made of dog heartworm, Dirofilaria immitis. The compounds of formula (I) are highly effective against those parasites.
Furthermore, the compounds of formula (I) are suitable for controlling parasites that are pathogens of humans, among which, as typical representatives occurring in the digestive tract, mention should be made of those of the species Ancylostoma, Necator, Ascaris, Strongyloides, Trichinella, Capillaria, Trichuris and Enterobius. The compounds of the present invention are also effective against parasites of the species Wuchereria, Brugia, Onchocerca and Loa from the family of the Filariidae, which occur in the blood, in tissue and various organs, and also against Dracunculus and parasites of the species Strongyloides and Trichinella, which infect especially the gastrointestinal tract.
In the area of crop protection, the compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly dilutable solutions, dilute emulsions, soluble powders, granules, and also encapsulations in polymer substances. As with the nature of the compositions, the methods of application are selected in accordance with the intended objectives and the prevailing circumstances.
The invention relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersibie powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising at least one of the active ingredients of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances. They are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, for example with solvents, solid carriers, and optionally surface-active compounds (surfactants). The active ingredient is used in those compositions in pure form: a solid active ingredient, for example, in a specific particle size, or preferably together with at least one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
As formulation adjuvants there are used, for example, solid carriers, solvents, stabilisers, "slow release" adjuvants, dyes and optionally surface-active substances (surfactants). Suitable carriers and adjuvants include all those substances customarily used in crop protection products, especially in snail and slug control products. Suitable adjuvants, such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and other adjuvants in the compositions used according to the invention, include e.g. those described in EP-A-736252, page 7, line 51, to page 8, line 39. They are included by reference in the subject matter of the present invention.
The compositions for use in crop protection generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient and from 1 to 99.9 % by weight, especially from 5 to 99.9 % by weight, of at least one solid or liquid adjuvant, it generally being possible for from 0 to 25 % by weight, especially from 0.1 to 20 %, of the compositions to consist of surfactants. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations, which have much lower active ingredient concentrations. Preferred compositions used in crop protection have especially the following compositions (% = % by weight):
Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % solvent: 5 to 98 %, preferably 70 to 85 %
Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 % Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 99 %, preferably 15 to 98 %
Granules: active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The anthelmintic compositions according to the invention for the control of animal parasites in and on warm-blooded organisms generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compound of formula (I), from 99.9 to 1 % by weight, especially from 99.8 to 5 % by weight, of a solid or liquid auxiliary, which includes from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
Preferred forms of administration for use in warm-blooded organisms for controlling helminths include solutions, emulsions, suspensions (drenches), feed additives, powders, tablets including effervescent tablets, boli, capsules, micro-encapsulations and pour-on formulations, it being necessary to ensure that the formulation adjuvants are physiologically tolerable.
Suitable solvents in the use of formulations for controlling animal parasites are, for example: alcohols, e.g. ethanol, propanol or butanol, and glycols and ethers and esters thereof, e.g. propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, e.g. cyclohexanone, isophorone or diacetone alcohol, strong polar solvents, e.g. N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide or water, vegetable oils, e.g. rapeseed oil, castor oil, coconut oil or soybean oil, and also, where appropriate, silicone oils.
Suitable binders for tablets and boli are chemically modified natural polymeric substances soluble in water or in alcohol, for example starch, cellulose or protein derivatives (e.g. methylcellulose, carboxymethylcellulose, ethyl hydroxyethylcellulose, proteins such as zein, gelatin and the like) and synthetic polymers, e.g. polyvinyl alcohol, polyvinylpyrrolidone etc.. Tablets also comprise fillers (e.g. starch, microcrystalline cellulose, sugar, lactose etc.), lubricants and disintegrants. When the anthelmintic compositions are in the form of feed concentrates, there are used as carriers, for example, performance feeds, feed grains or protein concentrates. Such feed concentrates or compositions can also comprise, besides the active ingredients, auxiliaries, vitamins, antibiotics, chemotherapeutic agents or other pesticides, especially bacteriostatics, fungistatics, coccidiostatics and also hormone preparations, substances having an anabolic action or substances that promote growth, that influence the quality of meat of slaughtered animals or that are useful in some other way for the organism. When the compositions or the compounds of formula (I) contained therein are added directly to the feed or drinking troughs, the final feed or drinking troughs contain the active ingredients in a concentration of preferably from 0.0005 to 0.02 % by weight (5-200 ppm).
The compounds of formula (I) according to the invention can be used alone or in combination with other biocides. For example, in order to enhance the effect they can be combined with pesticides having the same direction of action or, in order to broaden the spectrum of activity, they can be combined with substances having a different direction of action. It can also be of advantage to add so-called 'repellents'. Where it is desired to extend the spectrum of activity to endoparasites, e.g. worms, the compounds of formula (I) are advantageously combined with substances having endoparasiticidal properties. They can, of course, also be used in combination with anti-bacterial agents. Since the compounds of formula (I) are "adulticides", i.e. since they are effective especially against the mature stages of target parasites, the addition of pesticides which are more effective against the juvenile stages of the parasites may be very advantageous, since in this way the major portion of those parasites that cause large-scale economic damage will be reached, significantly contributing, moreover, to the avoidance of the formation of resistance. Some combinations may also result in synergistic effects, that is to say the overall amount of active substance used can be reduced, which is desirable from an ecological standpoint. Preferred groups of combination partners and especially preferred combination partners are mentioned hereinbelow; the combinations may comprise, in addition to a compound of formula (I), one or more of such partners.
Suitable mixing partners for use in crop protection and for use in controlling endo- and ectoparasites on warm-blooded organisms are biocides, for example the insecticides and acaricides mentioned hereinbelow and sufficiently known to the person skilled in the art which have a different mechanism of action, for example chitin synthesis inhibitors, growth regulators; active ingredients that act in the same manner as juvenile hormones; active ingredients that act as adulticides; broad-spectrum insecticides, broad-spectrum acaricides, and nematicides; and also the sufficiently known anthelmintics, and substances repelling insects and/or Acarina, the said repellents and detachers.
Examples of suitable insecticides and acaricides are azamethiphos; chlorfenvinphos; cyper- methrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; jodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from the Bacillus thuringiensis strain GC91 or from the strain NCTC11821; pymetrozine; bromopropylate; methoprene; disulfuton; quinalphos; tau-fluvalinate; thio- cyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb; bifenthrin; buprofezin; carbo- furan; dibutylaminothio; cartap; chlorfluazuron; chlorpyrifos; cyfluthrin; lambda-cyhalothrin; alpha-cypermethrin; zeta-cypermethrin; deltamethrin; diflubenzuron; endosulfan; ethio- fencarb; fenitrothion; fenobucarb; fenvalerate; formothion; methiocarb; heptenophos; imida- cloprid; isoprocarb; methamidophos; methomyl; mevinphos; parathion; parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron; terbufos; triazamate; fenobucarb; tebu- fenozide; fipronil; beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; fenazaquin; pyripro- xyfen; pyrimidifen; nitenpyram; acetamiprid; avermectin Bi (abamectin); emamectin; ema- mectin benzoate; spinosad; a plant extract that is active against insects; a preparation comprising nematodes which is active against insects; a preparation obtainable from Bacillus subtilis; a preparation comprising fungi which is active against insects; a preparation comprising viruses which is active against insects; chlorfenapyr; acephate; acrinathrin; alany- carb; alphamethrin; amitraz; Az 60541 ; azinphos A; azinphos M; azocyclotin; bendiocarb; bensultap; beta-cyfluthrin; BPMC; brofenprox; bromophos A; bufencarb; butocarboxin; butylpyridaben; cadusafos; carbaryl; carbophenothion; chloethocarb; chlorethoxyfos; chlor- mephos; cis-resmethrin; clocythrin; clofentezine; cyanophos; cycloprothrin; cyhexatin; demeton M; demeton S; demeton-S-methyl; dichlofenthion; dicliphos; diethion; dimethoate; dimethylvinphos; dioxathion; edifenphos; esfenvalerate; ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos; fenbutatin oxide; fenothiocarb; fenpropathrin; fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinate; flufenoxuron; flufenprox; fonophos; fosthiazate; fubfenprox; HCH; hexaflumuron; hexythiazox; IKI-220; iprobenfos; isofenphos; isoxathion; ivermectin; malathion; mecarbam; mesulfenphos; metaldehyde; metolcarb; milbemectin; moxidectin; naled; NC 184; omethoate; oxamyl; oxydemeton M; oxydeprofos; permethrin; phenthoate; phorate; phosmet; phoxim; pirimiphos M; pirimiphos E; promecarb; propaphos; prothiofos; prothoate; pyrachlophos; pyrada-phenthion; pyresmethrin; pyrethrum; tebu- fenozide; salithion; sebufos; sulfotep; sulprofos; tebufenpyrad; tebupirimphos; tefluthrin; temephos; terbam; tetrachlorvinphos; thiacloprid; thiafenox; thiamethoxam; thiodicarb; thiofanox; thionazin; thuringiensin; tralomethrin; triarthene; triazophos; triazuron; trichlorfon; triflumuron; trimethacarb; va idothion; xylylcarb; Yl 5301/5302; zetamethrin; DPX-MP062 - indoxacarb; methoxyfenozide; bifenazate; XMC (3,5-xylyl methylcarbamate); or the fungus pathogen Metarhizium Anisopliae. The mentioned mixing partners are very well known to persons skilled in the art. Most are described in various editions of The Pesticide Manual, The British Crop Protection Council, London, while others are described in various editions of The Merck Index, Merck & Co., Inc., Rahway, New Jersey, USA, or in the patent literature.
Examples of suitable anthelmintics that can be added to the compositions are mentioned hereinbelow, a number of the examples thereof having, in addition to anthelmintic activity, also an insecticidal and acaricidal activity, some of them already being mentioned in the list above:
(A1) praziquantel = 2-cyclohexylcarbonyl-4-oxo-1 ,2,3,6,7,11b-hexahydro-4H-pyrazino[2,1- jisoquinoline (A2) closantel = 3,5-diiodo-N-[5-chloro-2-methyl-4-(a-cyano-4-chlorobenzyl)phenyl]salicyl- amide (A3) triclabendazole = 5-chloro-6-(2,3-dichlorophenoxy)-2-methylthio-1 H-benzimidazole (A4) ievamjsoj = L-(-)-2,3,5,6-tetrahydro-6-phenylimidazo[2,1b]thiazole (A5) mebendazole = (5-benzoyl-1H-benzimidazol-2-yi)carbamic acid methyl ester (A6) omphalotin = a macrocyclic fermentation product of the fungus Omphalotus olearius described in WO 97/20857 (A7) abamectin = avermectin B1 (A8) ivermectin = 22,23-dihydroavermectin B1 (A9) moxidectin = 5-O-demethyl-28-deoxy-25-(1 ,3-dimethyl-1-butenyl)-6,28-epoxy-23-
(methoxyimino)-milbemycin B (A10) doramectin = 25-cyclohexyl-5-O-demethyl-25-de(1-methylpropyl)-avermectin A1a (AH) milbemectin = mixture of milbemycin A3 and milbemycin A4 (A12) milbemvcinoxim = 5-oxime of milbemectin
Examples of suitable repelling substances (repellents and detachers) are for instance:
(R1) DEET (N,N-diethyl-m-toluamide)
(R2) KBR 3023 N-butyl-2-oxycarbonyl-(2-hydroxy)-piperidine
(R3) cvmiazol = N-2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene-2,4-xylidine Given what has been said above, a further substantial aspect of the present invention relates to combination preparations for the control of parasites on warm-blooded organisms, which combination preparations comprise, in addition to a compound of formula (I), at least one further active ingredient having the same direction of action or a different direction of action and at least one physiologically tolerable carrier. The present invention is not limited to two- component combinations.
The compositions according to the invention can be administered to the animals being treated by topical, peroral, parenteral or subcutaneous means, the compositions being in the form of solutions, emulsions, suspensions (drenches), powders, tablets, boli, capsules and pour-on formulations.
The pour-on or spot-on method comprises applying the compound of formula (I) to a locally defined area of the skin or coat, advantageously on the back of the neck or the backbone of the animal. This is carried out, for example, by applying a swab or spray of the pour-on or spot-on formulation to a relatively small area of the coat from where the active ingredient becomes distributed over a wide area of the coat almost automatically as a result of the spreading constituents of the formulation assisted by the movements of the animal.
Pour-on and spot-on formulations advantageously comprise carriers that promote rapid distribution over the surface of the skin or in the coat of the host animal and are generally termed spreading oils. There are suitable, for example, oily solutions; alcoholic and iso- propanolic solutions, e.g. solutions of 2-octyl-dodecanol or oleyl alcohol; solutions in esters of monocarboxylic acids, such as isopropyl myristate, isopropyl palmitate, lauric acid oxalic ester, oleic acid oleyl ester, oleic acid decyl ester, hexyl laurate, oleyl oleate, decyl oleate, capric acid esters of saturated fatty alcohols of chain length d2-C18; solutions of esters of dicarboxylic acids, such as dibutyl phthalate, diisopropyl isophthalate, adipic acid diisopropyl ester, di-n-butyl adipate or solutions of esters of aliphatic acids, e.g. glycols. It may be advantageous for a dispersant known from the pharmaceutical or cosmetic industry also to be present. Examples are 2-pyrrolidone, 2-(N-alkyl)pyrrolidone, acetone, polyethylene glycol and its ethers and esters, propylene glycol or synthetic triglycerides.
The oily solutions include e.g. vegetable oils, such as olive oil, groundnut oil, sesame oil, pine oil, linseed oil and castor oil. The vegetable oils may also be in epoxidised form. It is also possible to use paraffins and silicone oils. Generally a pour-on or spot-on formulation will contain from 1 to 20 % by weight of a compound of formula (I), from 0.1 to 50 % by weight dispersant and from 45 to 98.9 % by weight solvent.
The pour-on or spot-on method can be used especially advantageously for herd animals, such as cattle, horses, sheep and pigs, where it is difficult or time-consuming to treat all the animals orally or via injection. By virtue of its simplicity, this method can of course also be used for all other animals, including individual domestic animals and pets, and is very popular with the keepers of the animals because it can often be carried out without the expert assistance of a veterinary surgeon.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
Such formulations may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as other active ingredients for obtaining special effects.
The present invention relates also to such anthelmintic compositions employed by the end user.
In each of the methods according to the invention for controlling pests and in each of the pesticidal compositions according to the invention, the active ingredients of formula (I) can be used in any of their spatial configurations or mixtures thereof.
The invention also encompasses a method for the prophylactic protection of warm-blooded organisms, especially of productive livestock, domestic animals and pets, against parasitic helminths, which method comprises administering to the animals the active ingredient of formula (I) or active ingredient formulations prepared therefrom as an additive to the feed or to the drinking troughs or in solid or liquid form orally, by injection or parenterally. The invention also encompasses the compounds of formula (I) according to the invention for use in one of the mentioned methods.
The Examples that follow serve merely to illustrate the invention without limiting the invention, the expression 'active ingredient' denoting one of the substances listed in the Tables.
Preferred formulations for use in the control of parasites on warm-blooded organisms have the following compositions: (% = % by weight) 1. Granules a) b) active ingredient from Tables 1 or 2 5 % 10 % kaolin 94 % - highly disperse silicic acid 1 % - attapulgite 90 %
The active ingredient is dissolved in methylene chloride and sprayed onto the carrier, and the solvent is then evaporated off in vacuo. Such granules can be mixed into the animal feed.
2. Granules active ingredient from Tables 1 or 2 3 % polyethylene glycol (MW 200) 3 % kaolin 94 %
(MW = molecular weight)
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
3. Tablets and boli
I active ingredient from Tables 1 or 2 33.00 % methylcellulose 0.80 % highly disperse silicic acid 0.80 % maize starch 8.40 %
II crystalline lactose 22.50 % maize starch 17.00 % microcrystalline cellulose 16.50 % magnesium stearate 1.00 %
I Methylcellulose is stirred into water. After the material has swelled, silicic acid is stirred in and the mixture is homogeneously suspended. The active ingredient and maize starch are mixed. The aqueous suspension is incorporated into the resulting mixture and kneaded to a dough. The mass thereby obtained is granulated through a 12 M sieve and dried.
II AH 4 excipients are mixed well.
III The premixes obtained according to I and II are mixed and compressed into tablets or boli. 4. Iniectable formulations
A. Oilv vehicle (slow release)
1. active ingredient from Tables 1 or 2 0.1-1.0 g groundnut oil ad 100 ml
2. active ingredient from Tables 1 or 2 0.1-1.0 g sesame oil ad 100 ml
Preparation: The active ingredient is dissolved in a portion of the oil with stirring and optionally with gentle heating, and after cooling the solution is made up to the desired volume and sterile-filtered through a suitable 0.22 micron membrane filter.
B. Water-miscible solvent (medium rate of release) active ingredient from Tables 1 or 2 0.1-1.0 g
4-hydroxymethyl-1 ,3-dioxolane (glycerol formal) 40 g
1 ,2-propanediol ad 100 ml an active ingredient from Table 1 0.1 -1.0 g glycerol dimethyl ketal 40 g
1 ,2-propanediol ad 100 ml
Preparation: The active ingredient is dissolved in a portion of the solvent with stirring, and the solution is made up to the desired volume and sterile-filtered through a suitable 0.22 micron membrane filter.
C. Aqueous solubilisate (rapid release)
1. active ingredient from Tables 1 or 2 0.1-1.0 g polyethoxylated castor oil (40 ethylene oxide units) 10 g 1 ,2-propanediol 20 g benzyl alcohol i g aqua ad inject. ad 100 ml
2. active ingredient from Tables 1 or 2 0.1-1.0 g polyethoxylated sorbitan monooleate (20 ethylene oxide units) 8 g 4-hydroxymethyl-1 ,3-dioxolane (glycerol formal) 20 g benzyl alcohol i g aqua ad inject. ad 100 ml Preparation: The active ingredient is dissolved in the solvents and the surfactant, and the solution is made up to the desired volume with water. Sterile-filtration is then carried out through a suitable membrane filter of 0.22 micron pore diameter.
5. Pour-on
A. active ingredient from Tables 1 or 2 5 g isopropyl myristate 10 g isopropanol ad 100 ml
B. active ingredient from Tables 1 or 2 2 g hexyl laurate 5 g medium-chain triglycerides 15 g ethanol ad 100 ml
C. active ingredient from Tables 1 or 2 2 g oleyl oleate 5 g
N-methyl-pyrrolidone 40 g isopropanol ad 100 ml
The aqueous systems may preferably be used also for oral and/or intraruminal administration.
The compositions may also comprise further ingredients such as stabilisers, e.g. vegetable oils and epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilisers as well as other active ingredients for obtaining special effects.
It is also possible to add to the described compositions further biologically active substances or additives that have neutral behaviour towards the compounds of formula (I) and have no adverse effect on the host animal to be treated, and also mineral salts or vitamins.
The compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a specific particle size, or in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant(s). The invention relates also to those processes for the preparation of the compositions according to the invention and to the use of the compounds of the formula (I) in the preparation of those compositions.
The invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type. Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient. The rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
A preferred method of application in the area of crop protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question. However, the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
The compositions according to the invention are also suitable for protecting plant propagation material, including genetically modified propagation material, e.g. seed material, such as fruit, tubers or grains, or plant cuttings, from animal pests. The propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown. The compounds according to the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation. The formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing. The invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.
The following Examples serve to illustrate the invention. They do not limit the invention. The symbol 'h' stands for 'hour'. Preoaration examples
Preparation of N-(1-cvano-1-r2.3-dichlorophenoxymethvnethyl)-C- phenylmethanesulphonamide a) A mixture of 5 g of 2,3-dichlorophenol, 4 g of 2-chloroacetone, 4.7 g of anhydrous potassium carbonate and 450 mg of potassium iodide is refluxed in 50 ml of acetone for 6 h, then cooled to room temperature and filtered. The filtrate is evaporated. 1-(2,3-Dichloro-phen- oxy)acetone is obtained in this way. b) 6.5 g of 1-(2,3-dichlorophenoxy)acetone, 1.76 g of sodium cyanide and 2.4 g of ammonium chloride are added to a solution of 30 ml of 25% ammonia and the mixture is stirred at room temperature for 24 h. The crude product is then extracted from the mixture using ethyl acetate, and the organic phase is separated off, washed with water and saturated sodium chloride solution, dried using magnesium sulphate and evaporated. 2-Amino-3-(2,3-dichlorophenoxy)-2-methylpropionitrile is thus obtained. c) 5.2 g of α-toluenesulphonyl chloride are added to a mixture of 6.6 g of 2-amino-3-(2,3-di- chlorophenoxy)-2-methylpropionitrile and 4.86 g of ethyldiisopropylamines in 50 ml of methy- lene chloride and the mixture is stirred at room temperature for 24 h. The crude product is then extracted from the mixture with ethyl acetate, and the organic phase is separated off, washed with aqueous sodium bicarbonate and saturated sodium chloride solution, dried using magnesium sulphate and evaporated. The residue is purified by high-pressure column chromatography on silica gel using hexane/ethyl acetate (2:1). The title compound is thus obtained.
The substances mentioned in the table below can also be prepared analogously to the procedures described above. The values of the melting points are indicated in °C.
Table 1
Figure imgf000027_0001
No. R2 n (Y) phys. Data
1.1 CH3 0 H 1.2 CH3 0 2-F No. R2 n (Y) phys. Data
1.3 CH3 0 3-F
1.4 CH3 0 4-F
1.5 CH3 0 2-CI
1.6 CH3 0 3-CI
1.7 CH3 0 4-CI
1.8 CH3 0 2,3-CI2
1.9 CH3 0 2,4-CI2
1.10 CH3 0 2,5-CI2
1.11 CH3 0 2,6-CI2
1.12 CH3 0 3,4-CI2
Figure imgf000028_0001
1.14 CH3 0 3-CF3
1.15 CH3 0 4-CF3
1.16 CH3 1 H
1.17 CH3 1 2-F
1.18 CH3 1 3-F
1.19 CH3 1 4-F
Figure imgf000028_0002
1.21 CH3 1 3-CI
1.22 CH3 1 4-CI
1.23 CH3 1 2,3-CI2
1.24 CH3 1 2,4-CI2
1.25 CH3 1 2,5-CI2
1.26 CH3 1 2,6-CI2
1.27 CH3 1 3,4-CI2
1.28 CH3 1 3,5-CI2
1.29 CH3 1 3-CF3
1.30 CH3 1 4-CF3
1.31 C2H5 0 H
1.32 C2H5 0 2-F
Figure imgf000028_0003
1.34 C2H5 0 4-F No. R2 n (Y) phys. Data
1.35 C2H5 0 2-CI
1.36 C2H5 0 3-CI
1.37 C2H5 0 4-CI
1.38 C2H5 0 2,3-Cla
1.39 C2H5 0 2,4-CI2
1.40 C2H5 0 2,5-CI2
1.41 C2H5 0 2,6-CI2
1.42 C2H5 0 3,4-CI2
1.43 C2H5 0 3,5-CI2
1.44 C2H5 0 3-CF3
1.45 C2H5 0 4-CF3
1.46 C2H5 1 H
1.47 C2H5 1 2-F
1.48 C2H5 1 3-F
1.49 C2H5 1 4-F
1.50 C2H5 1 2-CI
1.51 C2H5 1 3-CI
1.52 C2H5 1 4-CI
1.53 C2H5 1 2,3-Cla
1.54 C2H5 1 2,4-CI2
1.55 C2H5 1 2,5-CI2
1.56 C2H5 1 2,6-CI2
1.57 C2H5 1 3,4-CI2
1.58 C2H5 1 3,5-CI2
1.59 C2H5 1 3-CF3
1.60 C2H5 1 4-CF3
1.61 n-C3H7 0 H
1.62 n-C3H7 0 2-F
1.63 n-C3H 0 3-F
1.64 n-C3H7 0 4-F
1.65 n-C3H7 0 2-CI
1.66 n-C3H7 0 3-CI No. (Y) phys. Data
1.67 n-C3H7 0 4-CI
1.68 n-C3H7 0 2,3-CI2
1.69 n-C3H7 0 2,4-CI2
1.70 n-C3H7 0 2,5-CI2
1.71 n-C3H7 0 2,6-CI2
1.72 n-C3H7 0 3,4-CI2
1.73 n-C3H7 0 3,5-CI2
1.74 n-C3H7 0 3-CF3
1.75 n-C3H7 0 4-CF3
1.76 n-C3H7 H
1.77 n-C3H7 2-F
1.78 n-C3H7 3-F
1.79 n-C3H7 4-F
1.80 n-C3H7 2-CI
1.81 n-C3H7 3-CI
1.82 n-C3H7 4-CI
1.83 n-C3H7 2,3-CI2
1.84 n-C3H7 2,4-CI2
1.85 n-C3H7 2,5-CI2
1.86 n-C3H7 2,6-CI2
1.87 n-C3H7 3,4-CI2
1.88 n-C3H7 3,5-CI2
1.89 n-C3H7 3-CF3
1.90 n-C3H7 4-CF3
1.91 n-C4H9 0 H
1.92 n-C4H9 0 2-F
1.93 n-C4H9 0 3-F
1.94 n-C4H9 0 4-F
1.95 n-C4H9 0 2-CI
1.96 n-C4H9 0 3-CI
1.97 n-C4H9 0 4-CI
1.98 n-C4H9 0 2,3-Clz No. R2 (Y) phys. Data
1.99 n-C4H9 0 2,4-CI2
1.100 n-C4H9 0 2,5-CI2
1.101 n-C4H9 0 2,6-CI2
1.102 n-C4H9 0 3,4-CI2
1.103 n-C4H9 0 3,5-CI2
1.104 n-C4H9 0 3-CF3
1.105 n-C4H9 0 4-CF3
1.106 n-C H9 H
1.107 n-C H9 2-F
1.108 n-C4H9 3-F
1.109 n-C4H9 4-F
1.110 n-C4H9 2-CI
1.111 n-C4H9 3-CI
1.112 n-C4H9 4-CI
1.113 n-C4H9 2,3-CI2
1.114 n-C4H9 2,4-CI2
1.115 n-C4H9 2,5-CI2
1.116 n-C4H9 2,6-CI2
1.117 n-C H9 3,4-CI2
1.118 n-C4H9 3,5-CI2
1.119 n-C4H9 3-CF3
1.120 n-C H9 4-CF3
Figure imgf000031_0001
1.122 CH2C6H5 0 2-F
1.123 CH2C8H5 0 3-F
Figure imgf000031_0002
1.125 CH2C6H5 0 2-CI
1.126 CH2C6H5 0 3-CI
1.127 CH2C6H5 0 4-CI
Figure imgf000031_0003
1.130 CH2C6H5 0 2,5-CI2 No. n (Y) phys. Data
1.131 CH2C8H5 0 2,6-CI2
Figure imgf000032_0001
1.133 CHjjCβHs 0 3,5-CI2
Figure imgf000032_0002
1.137 CH2C8H5 2-F
1.138 CH2C8H5 3-F
1.139 CH2CeH5 4-F
1.140 CH2CeH5 2-CI
Figure imgf000032_0003
1.145 CHjjCβHs 2,5-CI2
1.146 CH2C6Hδ 2,6-CI2
Figure imgf000032_0004
1.154 CδHδ 0 4-F
1.155 C6Hs 0 2-CI
1.156 C6H5 0 3-CI
1.157 C6H5 0 4-CI
Figure imgf000032_0005
1.159 C6H5 0 2,4-Cla
Figure imgf000032_0006
No. R2 n (Y) phys. Data
1.164 CeHs 0 3-CF3
Figure imgf000033_0002
1.170 C6H5 2-CI
1.171 C6Hδ 3-CI
Figure imgf000033_0003
1.175 C6H5 2,5-CI2
Figure imgf000033_0004
1.177 C6H5 3,4-CI2
Figure imgf000033_0005
1.180 C6H5 4-CF3
1.181 C6H4-4-CH3 0 H
1.182 C6H4-4-CH3 0 2-F
1.183 C6H4-4-CH3 0 3-F
1.184 C6H4-4-CH3 0 4-F
1.185 C6H4-4-CH3 0 2-CI
1.186 C6H4-4-CH3 0 3-CI
1.187 C6H4-4-CH3 0 4-CI
1.188 C6H4-4-CH3 0 2,3-CI2
1.189 C6H4-4-CH3 0 2,4-CI2
1.190 C6H4-4-CH3 0 2,5-CI2
1.191 C6H4-4-CH3 0 2,6-CI2
1.192 C6H4-4-CH3 0 3,4-CI2
1.193 C6H4-4-CH3 0 3,5-CI2
1.194 C6H4-4-CH3 0 3-CF3 No. (Y) phys. Data
1.195 C6H4-4-CH3 0 4-CF3
1.196 CeH4-4-CH3 H
1.197 C6H4-4-CH3 2-F
1.198 C6H4-4-CH3 3-F
1.199 C6H4-4-CH3 4-F
1.200 C6H4-4-CH3 2-CI
1.201 C6H4-4-CH3 3-CI
1.202 C6H4-4-CH3 4-CI
1.203 C6H4-4-CH3 2,3-CI2
1.204 C6H4-4-CH3 2,4-CI2
1.205 C6H4-4-CH3 2,5-CI2
1.206 C6H4-4-CH3 2,6-CI2
1.207 C6H4-4-CH3 3,4-CI2
1.208 CeH4-4-CH3 3,5-CI2
1.209 C6H4-4-CH3 3-CF3
1.210 C6H4-4-CH3 4-CF3
1.211 C6H4-4-F 0 H
1.212 C6H4-4-F 0 2-F
1.213 C6H4-4-F 0 3-F
1.214 C6H4-4-F 0 4-F
1.215 C6H4-4-F 0 2-CI
1.216 C6H4-4-F 0 3-CI
1.217 C6H4-4-F 0 4-CI
1.218 C6H4-4-F 0 2,3-CI2
1.219 C6H4-4-F 0 2,4-CI2
1.220 C6H4-4-F 0 2,5-CI2
1.221 C6H4-4-F 0 2,6-CI2
1.222 C6H4-4-F 0 3,4-CI2
1.223 C6H4-4-F 0 3,5-CI2
1.224 C6H4-4-F 0 3-CF3
1.225 C6H4-4-F 0 4-CF3
1.226 C6H4-4-F 1 H No. (Y) phys. Data
1.227 C6H4-4-F 2-F
1.228 C6H4-4-F 3-F
1.229 C6H4-4-F 4-F
1.230 C6H4-4-F 2-CI
1.231 C6H4-4-F 3-CI
1.232 C6H4-4-F 4-CI
1.233 C6H4-4-F 2,3-CI2
1.234 C6H4-4-F 2,4-CI2
1.235 C6H4-4-F 2,5-CI2
1.236 C6H4-4-F 2,6-CI2
1.237 C6H4-4-F 3,4-CI2
1.238 C6H4-4-F 3,5-CI2
1.239 C6H4-4-F 3-CF3
1.240 C6H4-4-F 4-CF3
1.241 C6H4-4-CI 0 H
1.242 C6H4-4-CI 0 2-F
1.243 C6H4-4-CI 0 3-F
1.244 C6H4-4-CI 0 4-F
1.245 C6H4-4-CI 0 2-CI
1.246 C6H4-4-CI 0 3-CI
1.247 C6H4-4-CI 0 4-CI
1.248 C6H4-4-CI 0 2,3-CI2
1.249 C6H4-4-CI 0 2,4-CI2
1.250 C6H4-4-CI 0 2,5-CI2
1.251 C6H4-4-CI 0 2,6-CI2
1.252 C6H4-4-CI 0 3,4-CI2
1.253 C6H4-4-CI 0 3,5-CI2
1.254 C6H4-4-CI 0 3-CF3
1.255 C6H4-4-CI 0 4-CF3
1.256 C6H4-4-CI 1 H
1.257 C6H4-4-CI 1 2-F
1.258 C6H4-4-CI 1 3-F No. (Y) phys. Data
1.259 C6H4-4-CI 4-F
1.260 C6H4-4-CI 2-CI
1.261 C6H4-4-CI 3-CI
1.262 C6H4-4-CI 4-CI
1.263 C6H4-4-CI 2,3-CI2
1.264 C6H4-4-CI 2,4-CI2
1.265 C6H4-4-CI 2,5-CI2
1.266 C6H4-4-CI 2,6-CI2
1.267 C6H4-4-CI 3,4-CI2
1.268 C6H4-4-CI 3,5-CI2
1.269 C6H4-4-CI 3-CF3
1.270 C6H4-4-CI 4-CF3
1.271 C6H4-4-Br 0 H
1.272 C6H4-4-Br 0 2-F
1.273 C6H4-4-Br 0 3-F
1.274 C6H4-4-Br 0 4-F
1.275 C6H4-4-Br 0 2-CI
1.276 C6H4-4-Br 0 3-CI
1.277 C6H4-4-Br 0 4-CI
1.278 C6H4-4-Br 0 2,3-CI2
1.279 C6H4-4-Br 0 2,4-CI2
1.280 C6H4-4-Br 0 2,5-CI2
1.281 C6H4-4-Br 0 2,6-CI2
1.282 C6H4-4-Br 0 3,4-CI2
1.283 C6H4-4-Br 0 3,5-CI2
1.284 C6H4-4-Br 0 3-CF3
1.285 C6H4-4-Br 0 4-CF3
1.286 C6H4-4-Br H
1.287 C6H4-4-Br 2-F
1.288 C6H4-4-Br 3-F
1.289 C6H4-4-Br 4-F
1.290 C6H4-4-Br 2-CI No. R2 n (Y) phys. Data
1.291 C6H4-4-Br 3-CI
1.292 C6H4-4-Br 4-CI
1.293 C6H4-4-Br 2,3-CI2
1.294 C6H4-4-Br 2,4-Cla
1.295 C6H4-4-Br 2,5-CI2
1.296 C6H4-4-Br 2,6-Cla
1.297 C6H4-4-Br 3,4-Clz
1.298 C6H4-4-Br 3,5-CI2
1.299 C6H4-4-Br 3-CF3
1.300 C6H4-4-Br 4-CF3
1.301 C6H4-4-OCH3 0 H
1.302 C6H4-4-OCH3 0 2-F
1.303 C6H4-4-OCH3 0 3-F
1.304 C6H4-4-OCH3 0 4-F
1.305 C6H4-4-OCH3 0 2-CI
1.306 C6H4-4-OCH3 0 3-CI
1.307 C6H4-4-OCH3 0 4-CI
1.308 C6H4-4-OCH3 0 2,3-CI2
1.309 C6H4-4-OCH3 0 2,4-CI2
1.310 C6H4-4-OCH3 0 2,5-CI2
1.311 C6H4-4-OCH3 0 2,6-CI2
1.312 C6H4-4-OCH3 0 3,4-CI2
1.313 C6H4-4-OCH3 0 3,5-CI2
1.314 C6H4-4-OCH3 0 3-CF3
1.315 C6H4-4-OCH3 0 4-CF3
1.316 C6H4-4-OCH3 H
1.317 C6H4-4-OCH3 2-F
1.318 C6H4-4-OCH3 3-F
1.319 C6H4-4-OCH3 4-F
1.320 C6H4-4-OCH3 2-CI
1.321 C6H4-4-OCH3 3-CI
1.322 C6H4-4-OCH3 4-CI No. (Y) phys. Data
1.323 C6H4-4-OCH3 2,3-CI2
1.324 C6H4-4-OCH3 2,4-CI2
1.325 C6H4-4-OCH3 2,5-CI2
1.326 C6H4-4-OCH3 2,6-CI2
1.327 C6H4-4-OCH3 3,4-CI2
1.328 C6H4-4-OCH3 3,5-CI2
1.329 C6H4-4-OCH3 3-CF3
1.330 C6H4-4-OCH3 4-CF3
1.331 C6H4-2-CF3 0 H
1.332 C6H4-2-CF3 0 2-F
1.333 C6H4-2-CF3 0 3-F
1.334 C6H4-2-CF3 0 4-F
1.335 C6H4-2-CF3 0 2-CI
1.336 C6H4-2-CF3 0 3-CI
1.337 C6H4-2-CF3 0 4-CI
1.338 C6H4-2-CF3 0 2,3-CI2
1.339 C6H4-2-CF3 0 2,4-CI2
1.340 C6H4-2-CF3 0 2,5-CI2
1.341 C6H4-2-CF3 0 2,6-CI2
1.342 C6H4-2-CF3 0 3,4-CI2
1.343 C6H4-2-CF3 0 3,5-CI2
1.344 C6H4-2-CF3 0 3-CF3
1.345 C6H4-2-CF3 0 4-CF3
1.346 C6H4-2-CF3 H
1.347 C6H4-2-CF3 2-F
1.348 C6H4-2-CF3 3-F
1.349 C6H4-2-CF3 4-F
1.350 C6H4-2-CF3 2-CI
1.351 C6H4-2-CF3 3-CI
1.352 C6H4-2-CF3 4-CI
1.353 C6H4-2-CF3 2,3-CI2
1.354 C6H4-2-CF3 2,4-CI2 No. Ra (Y) phys. Data
1.355 CβH -2-CF3 2,5-CI2 1.356 CeH -2-CF3 2,6-CI2 1.357 CeH -2-CF3 3,4-CI2 1.358 CeH -2-CF3 3,5-CI2
Figure imgf000039_0001
1.360 CeH4-2-CF3 4-CF3 1.361 CδH4-3-CF3 0 H 1.362 C6H4-3-CF3 0 2-F 1.363 C8H -3-CF3 0 3-F 1.364 CeH4-3-CF3 0 4-F 1.365 CδH4-3-CF3 0 2-CI 1.366 C6H4-3-CF3 0 3-CI 1.367 CeH4-3-CF3 0 4-CI 1.368 CβH -3-CF3 0 2,3-CI2 1.369 CβH4-3-CF3 0 2,4-CI2 1.370 CeH4-3-CF3 0 2,5-CI2 1.371 CβH4-3-CF3 0 2,6-CI2 1.372 CeH4-3-CF3 0 3,4-Clz 1.373 CeH -3-CF3 0 3,5-CI2 1.374 CeH4-3-CF3 0 3-CF3 1.375 CδH4-3-CF3 0 4-CF3 1.376 CeH -3-CF3 H 1.377 CeH4-3-CF3 2-F 1.378 CeH4-3-CF3 3-F 1.379 CeH -3-CF3 4-F 1.380 CeH4-3-CF3 2-CI 1.381 CδH -3-CF3 3-CI 1.382 CeH4-3-CF3 4-CI 1.383 C6H4-3-CF3 2,3-CI2 1.384 CδH -3-CF3 2,4-CI2 1.385 CeH -3-CF3 2,5-CI2 1.386 CβH4-3-CF3 2,6-CI2 No. (Y) phys. Data
1.387 CeH4-3-CF3 1 3,4-CI2
1.388 C8H -3-CF3 1 3,5-CI2
1.389 CeH -3-CF3 1 3-CF3
1.390 C8H -3-CF3 1 4-CF3
1.391 C6H4-4-CF3 0 H
1.392 C6H4-4-CF3 0 2-F
1.393 C6H4-4-CF3 0 3-F
1.394 C6H4-4-CF3 0 4-F
1.395 C6H4-4-CF3 0 2-CI
1.396 C6H4-4-CF3 0 3-CI
1.397 C6H4-4-CF3 0 4-CI
1.398 C6H4-4-CF3 0 2,3-CI2
1.399 C6H4-4-CF3 0 2,4-CI2
1.400 C6H4-4-CF3 0 2,5-CI2
1.401 C6H4-4-CF3 0 2,6-CI2
1.402 C6H4-4-CF3 0 3,4-CI2
1.403 C6H4-4-CF3 0 3,5-CI2
1.404 C6H4-4-CF3 0 3-CF3
1.405 C6H4-4-CF3 0 4-CF3
1.406 C6H4-4-CF3 H
1.407 C6H4-4-CF3 2-F
1.408 C6H4-4-CF3 3-F
1.409 C6H4-4-CF3 4-F
1.410 C6H4-4-CF3 2-CI
1.411 C6H4-4-CF3 3-CI
1.412 C6H4-4-CF3 4-CI
1.413 C6H4-4-CF3 2,3-CI2
1.414 C6H4-4-CF3 2,4-Cla
1.415 C6H4-4-CF3 2,5-CI2
1.416 C6H4-4-CF3 2,6-CI2
1.417 C6H4-4-CF3 3,4-CI2
1.418 C6H4-4-CF3 3,5-CI2
Figure imgf000041_0001
No. n (Y) phys. Data
1.451 C6H2-2,3,4-CI3 0 H
1.452 C6H2-2,3,4-CI3 0 2-F
1.453 C6H2-2,3,4-CI3 0 3-F
1.454 C6H2-2,3,4-CI3 0 4-F
1.455 C6H2-2,3,4-CI3 0 2-CI
1.456 C6H2-2,3,4-CI3 0 3-CI
1.457 C6H2-2,3,4-CI3 0 4-CI
1.458 C6H2-2,3,4-CI3 0 2,3-CI2
1.459 C6H2-2,3,4-CI3 0 2,4-CI2
1.460 C6H2-2,3,4-CI3 0 2,5-CI2
1.461 C6H2-2,3,4-CI3 0 2,6-CI2
1.462 C6H2-2,3,4-CI3 0 3,4-CI2
1.463 C6H2-2,3,4-Cl3 0 3,5-CI2
1.464 C6H2-2,3,4-CI3 0 3-CF3
1.465 C6H2-2,3,4-CI3 0 4-CF3
1.466 C6H2-2,3,4-CI3 H
1.467 C6H2-2,3,4-CI3 2-F
1.468 C6H2-2,3,4-CI3 3-F
1.469 C6H2-2,3,4-CI3 4-F
1.470 C6H2-2,3,4-CI3 2-CI
1.471 C6H2-2,3,4-CI3 3-CI
1.472 C6H2-2,3,4-CI3 4-CI
1.473 C6H2-2,3,4-CI3 2,3-CI2
1.474 C6H2-2,3,4-CI3 2,4-Clz
1.475 C6H2-2,3,4-CI3 2,5-CI2
1.476 C6H2-2,3,4-CI3 2,6-CI2
1.477 C6H2-2,3,4-CI3 3,4-CI2
1.478 C6H2-2,3,4-CI3 3,5-CI2
1.479 C6H2-2,3,4-CI3 3-CF3
1.480 C6H2-2,3,4-CI3 4-CF3
1.481 C6H2-2,4,5-CI3 0 H
1.482 C6H2-2,4,5-CI3 0 2-F No. n (Y) phys. Data
1.483 C6H2-2,4,5-CI3 0 3-F
1.484 C6H2-2,4,5-CI3 0 4-F
1.485 C6H2-2,4,5-CI3 0 2-CI
1.486 C6H2-2,4,5-CI3 0 3-CI
1.487 C6H2-2,4,5-CI3 0 4-CI
1.488 C6H2-2,4,5-CI3 0 2,3-CI2
1.489 C6H2-2,4,5-CI3 0 2,4-CI2
1.490 C6H2-2,4,5-CI3 0 2,5-CI2
1.491 C6H2-2,4,5-CI3 0 2,6-CI2
1.492 C6H2-2,4,5-CI3 0 3,4-CI2
1.493 C6H2-2,4,5-CI3 0 3,5-CI2
1.494 C6H2-2,4,5-CI3 0 3-CF3
1.495 C6H2-2,4,5-CI3 0 4-CF3
1.496 C6H2-2,4,5-CI3 H
1.497 C6H2-2,4,5-CI3 2-F
1.498 C6H2-2,4,5-CI3 3-F
1.499 C6H2-2,4,5-CI3 4-F
1.500 C6H2-2,4,5-CI3 2-CI
1.501 C6H2-2,4,5-CI3 3-CI
1.502 C6H2-2,4,5-CI3 4-CI
1.503 C6H2-2,4,5-CI3 2,3-CI2
1.504 C6H2-2,4,5-CI3 2,4-Cfe
1.505 C6H2-2,4,5-CI3 2,5-CI2
1.506 C6H2-2,4,5-CI3 2,6-CI2
1.507 C6H2-2,4,5-CI3 3,4-CI2
1.508 C6H2-2,4,5-CI3 3,5-CI2
1.509 C6H2-2,4,5-CI3 3-CF3
1.510 C6H2-2,4,5-CI3 4-CF3
1.511 C6H3-2-OCH3-5-Br 0 H
1.512 C6H3-2-OCH3-5-Br 0 2-F
1.513 C6H3-2-OCH3-5-Br 0 3-F
1.514 C6H3-2-OCH3-5-Br 0 4-F No. R2 n (Y) phys. Data
1.515 C6H3-2-OCH3-5-Br 0 2-CI
1.516 C6H3-2-OCH3-5-Br 0 3-CI
1.517 C6H3-2-OCH3-5-Br 0 4-CI
1.518 C6H3-2-OCH3-5-Br 0 2,3-CI2
1.519 C6H3-2-OCH3-5-Br 0 2,4-CI2
1.520 C6H3-2-OCH3-5-Br 0 2,5-CI2
1.521 C6H3-2-OCH3-5-Br 0 2,6-CI2
1.522 C6H3-2-OCH3-5-Br 0 3,4-CI2
1.523 C6H3-2-OCH3-5-Br 0 3,5-CI2
1.524 C6H3-2-OCH3-5-Br 0 3-CF3
1.525 C6H3-2-OCH3-5-Br 0 4-CF3
1.526 C6H3-2-OCH3-5-Br 1 H
1.527 C6H3-2-OCH3-5-Br 1 2-F
1.528 C6H3-2-OCH3-5-Br 1 3-F
1.529 C6H3-2-OCH3-5-Br 1 4-F
1.530 C6H3-2-OCH3-5-Br 1 2-CI
1.531 C6H3-2-OCH3-5-Br 1 3-CI
1.532 C6H3-2-OCH3-5-Br 1 4-CI
1.533 C6H3-2-OCH3-5-Br 1 2,3-CI2
1.534 C6H3-2-OCH3-5-Br 1 2,4-CI2
1.535 C6H3-2-OCH3-5-Br 1 2,5-CI2
1.536 C6H3-2-OCH3-5-Br 1 2,6-CI2
1.537 C6H3-2-OCH3-5-Br 1 3,4-CI2
1.538 C6H3-2-OCH3-5-Br 1 3,5-CI2
1.539 C6H3-2-OCH3-5-Br 1 3-CF3
1.540 C6H3-2-OCH3-5-Br 1 4-CF3
1.541 1-naphthyl 0 H
1.542 1-naphthyl 0 2-F
1.543 1-naphthyl 0 3-F
1.544 1-naphthyl 0 4-F
1.545 1-naphthyl 0 2-CI
1.546 1-naphthyl 0 3-CI No. R2 (Y) phys. Data
1.547 1 -naphthyl 0 4-CI
1.548 1 l-naphthyl 0 2,3-CI2
1.549 1 I -naphthyl 0 2,4-CI2
1.550 1 l-naphthyl 0 2,5-CI2
1.551 l-naphthyl 0 2,6-CI2
1.552 ' l-naphthyl 0 3,4-CI2
1.553 l-naphthyl 0 3,5-CI2
1.554 l-naphthyl 0 3-CF3
1.555 l-naphthyl 0 4-CF3
1.556 l-naphthyl H
1.557 • l-naphthyl 2-F
1.558 l-naphthyl 3-F
1.559 l-naphthyl 4-F
1.560 l-naphthyl 2-CI
1.561 l-naphthyl 3-CI
1.562 1-naphthyl 4-CI
1.563 l-naphthyl 2,3-CI2
1.564 l-naphthyl 2,4-CI2
1.565 1-naphthyl 2,5-CI2
1.566 l-naphthyl 2,6-CI2
1.567 l-naphthyl 3,4-CI2
1.568 1-naphthyl 3,5-CI2
1.569 l-naphthyl 3-CF3
1.570 1 -naphthyl 4-CF3
Bioloαical examples
A. Control of animal parasites
Example B.1. In-vivo test against Trichostronqylus colubriformis and Haemonchus contortus in Mongolian gerbils (Meriones unαuiculatus) on peroral administration
Six to eight week-old Mongolian gerbils are infected by artificial feeding with about 2000 larvae each of the 3rd stage of T. colubriformis and H. contortus. 6 days after infection, the gerbils are lightly anaesthetized with N2O and treated by peroral administration with the test compounds, dissolved in a mixture of 2 parts of DMSO and 1 part of polyethylene glycol (PEG 300), using amounts of 100, 32 and 10 - 0.1 mg/kg. On day 9 (3 days after treatment), when most of the H.contortus larvae of the late 4th stage and most of the T. colubriformis are immature adults, the gerbils are killed to count the worms. The efficacy is calculated in % reduction of the number of worms in each gerbil by comparison with the geometric mean of the number of worms of 8 infected and untreated gerbils.
A strong reduction of the nematode attack is achieved in this test with compounds of the formula (I).
B. Control of plant pests
Example B.2: Action against Heliothis virescens caterpillars
Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising
400 ppm of active ingredient and, after the spray-coating has dried, are populated with
10 caterpillars of Heliothis virescens in the first stage and then placed in a plastics container.
Evaluation is carried out 6 days later. The percentage reduction in population and in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
The compounds of the Tables exhibit good activity against Heliothis virescens in this test.
Example B.3: Action against Plυtella xylostella caterpillars
Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising
400 ppm of active ingredient and, after the spray-coating has dried, are populated with
10 caterpillars of Plutella xylostella in the third stage and then placed in a plastics container.
Evaluation is carried out 3 days later. The percentage reduction in population and in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
The compounds of the Tables exhibit good activity against Plutella xylostella. Example B.4: Action against Diabrotica balteata larvae
Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray-coating has dried, are populated with 10 larvae of Diabrotica balteata in the second stage and then placed in a plastics container. Evaluation is carried out 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants. The compounds of the Tables exhibit good activity against Diabrotica balteata in this test.

Claims

What is claimed is
1. Compound of the formula
Figure imgf000048_0001
in which
Ri is aryl or heteroaryl, in each case unsubstituted or mono- or polysubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ;
R2 is d-C6alkyl, halo-CrC6alkyl, C3-C8cycloalkyl, halo-C3-C8cycloalkyl, NHR8, aryl or heteroaryl, in each case unsubstituted or mono- or polysubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 , or pyrrolidinyl, piperidinyl, imidazolidinyl, piperazinyl, pyrazolidinyl, morpholinyl, indolinyl or isoindolinyl, in each case bonded via N;
R3 is hydrogen, C C6alkyl, halo-C C6alkyl, Cι-C6alkoxy-d-C6alkyl, benzyl, Cr C6alkylheteroaryl, d-C6alkoxycarbonyl or C1-C6alkylcarbonyl;
R4, R5 and R6 either independently of one another are hydrogen, halogen, C C6alkyl, halo- CrC6alkyl, d-Cealkoxy, halo-d-C6alkoxy, CrC6alkylthio, halo-d-C6alkylthio, C2-C6alkenyl, C2-C6alkynyl, unsubstituted or substituted C3-C8cycloalkyl, where the substituents are selected from the group consisting of halogen and Cι-C6alkyl, or unsubstituted or substituted phenyl, where the substituents are selected from the group consisting of halogen, C C6alkyl and phenyl; or R and R5, together with the carbon atoms to which they are bonded, are a five- to seven- membered, saturated or partially unsaturated heterocyclic ring having 1 to 2 heteroatoms from the group consisting of nitrogen, oxygen and sulphur;
R7 is halogen, d-C6alkyl, halo-CrC6alkyl, CrCealkoxy, halo-d-C6alkoxy, CrC6alkyIthio, halo-C C6alkylthio, C2-C6alkenyl, C2-C6alkynyl; aryl, phenylacetylenyl or heteroaryl, in each case unsubstituted or mono- or polysubstituted, where the substituents are in each case selected from the group consisting of halogen, nitro, cyano, Chalky!, halo-CrC6alkyl, d- C6alkoxy, halo-CrC6alkoxy, and can in each case be identical or different if their number is greater than 1; R8 is aryl which is unsubstituted or mono- to pentasubstituted, where the substituents are selected from the group consisting of halogen, nitro, cyano, Ci C6alkyl, halo-d-C6alkyl, d- C6alkoxy and halo-d-C6alkoxy, and can be identical or different if their number is greater than 1 ;
X is O, S, S(O) or S(O)2; and n is 0 or 1 ; and, where appropriate, E Z isomers, mixtures of E/Z isomers and/or tautomers thereof, in each case in free form or in salt form.
2. Compound of the formula (I) according to claim 1 , wherein R is aryl which is unsubstituted or mono- to pentasubstituted by R7, where the substitutents in each case can be identical or different if their number is greater than 1.
3. Compound of the formula (I) according to claim 1 , wherein Ri is aryl which is mono- to trisubstituted by R , where the substituents in each case can be identical or different if their number is greater than 1.
4. Compound of the formula (I) according to claim 1, wherein R2 is d-C6alkyl, halo-d- C6alkyl, aryl or heteroaryl which is in each case unsubstituted or mono- to polysubstituted by R7, where the substituents can in each case be identical or different if their number is greater than l.
5. Compound of the formula (I) according to claim 1, wherein R2 is d-C6alkyl, halo-Cr C6alkyl or aryl which is unsubstituted or mono- to pentasubstituted by R7) where the substituents can be identical or different if their number is greater than 1.
6. Compound of the formula (I) according to claim 1 , wherein R2 is aryl which is unsubstituted or mono- to trisubstituted by R7, where the substituents can be identical or different if their number is greater than 1.
7. Compound of the formula (I) according to claim 1 , wherein R3 is hydrogen or C C6alkyl.
8. Compound of the formula (I) according to claim 1 , wherein R3 is hydrogen or C1-C4alkyl.
9. Compound of the formula (I) according to claim 1 , wherein R3 is hydrogen.
10. Compound of the formula (I) according to claim 1, wherein R4, R5 and R6 independently of one another are hydrogen, d-C6alkyl, halo-d-C6alkyl, d-C6alkoxy, halo-d-Cealkoxy, C2- C6alkenyl, C2-C6-alkynyl, C3-C6cycloalkyl.
11. Compound of the formula (I) according to claim 1 , wherein R4, R5 and R6 independently of one another are hydrogen, C1-C alkyl, halo-d-C4alkyl or C3-C6cycloalkyl.
12. Compound of the formula (I) according to claim 1, wherein R4, R5 and R6 independently of one another are hydrogen or d-C2alkyl.
13. Compound of the formula (I) according to claim 1, wherein R7 is halogen, d-C4alkyl, halo-d-C alkyl, C1-C4-alkoxy, halo-C1-C4alkoxy; aryl or phenylacetylenyl, in each case unsubstituted or mono- or polysubstituted, where the substituents are selected from the group consisting of halogen, Cι-C6alkyl, halo-d-C6alkyl, d-C6alkoxy, halo-d-C6alkoxy, and can in each case be identical or different if their number is greater than 1.
14. Compound of the formula (I) according to claim 1, wherein R7 is halogen, d-C2alkyl, halo-d-C2alkyl, C1-C2alkoxy, halo-d-C2alkoxy.
15. Compound of the formula (I) according to claim 1, wherein R7 is halogen or halo-d- C2alkyl.
16. Compound of the formula (I) according to claim 1 , wherein R8 is unsubstituted or mono- to trisubstituted aryl, where the substituents are selected from the group consisting of halogen, d-C4alkyl, halo-Cι-C4alkyl, C C4alkoxy and halo-Cι-C4alkoxy, and can be identical or different if their number is greater than 1.
17. Compound of the formula (I) according to claim 1, wherein R8 is mono- to trisubstituted aryl, where the substituents are selected from the group consisting of halogen, CrC2alkyl, halo-d-C2alkyl, and halo-Cι-C2aIkoxy, and can be identical or different if their number is greater than 1.
18. Compound of the formula (I) according to claim 1 , wherein R8 is mono- or disubstituted aryl, where the substituents are selected from the group consisting of halogen and halo-Cr C2alkyl, and can be identical or different if their number is greater than 1.
19. Compound of the formula (I) according to claim 1 , wherein X is O or S.
20. Compound of the formula (I) according to claim 1 , wherein X is O.
21. Compound of the formula (I) according to claim 1 , wherein n is 1.
22. Compound of the formula (I) according to claim 1 , wherein Ri is aryl which is unsubstituted or mono- or pentasubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1; R2 is d-C6alkyl, halo-C C6alkyl, aryl or heteroaryl, in each case unsubstituted or mono- or polysubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ; R3 is hydrogen or d-C6alkyl; R , R5 and R6 independently of one another are hydrogen, Cι- C6alkyl, halo-C C6alkyl, d-Cealkoxy, halo-Cι-C6alkoxy, C2-C6alkenyl, C2-C6alkynyl, C3- C6cycloalkyl; R7 is halogen, CrC4alkyl, halo-C C4alkyl, CrC alkoxy, halo-Cι-C4alkoxy, aryl or phenylacetylenyl, in each case unsubstituted or mono- or polysubstituted, where the substituents are selected from the group consisting of halogen, d-C6alkyl, halo-d-C6alkyl, CrCealkoxy, halo-d-C6alkoxy, and in each case can be identical or different if their number is greater than 1 ; R8 is unsubstituted or mono- to trisubstituted aryl, where the substituents are selected from the group consisting of halogen, Cι-C4alkyl, halo-d-C alkyl, d-C alkoxy and halo-d-C4alkoxy, and can be identical or different if their number is greater than 1 ; X is O or S; and n is 1.
23. Compound of the formula (I) according to claim 1 , wherein R is aryl which is mono- or trisubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ; R2 is d-C6alkyl, halo-d-C6alkyl or aryl which is unsubstituted or mono- to pentasubstituted by R7, where the substituents can be identical or different if their number is greater than 1 ; R3 is hydrogen or d-C alkyl; R4, R5 and R6 independently of one another are hydrogen, d-C4alkyl, halo-Cι-C alkyl or C3-C6cycloalkyl; R7 is halogen, d- C2alkyl, halo-d-C2alkyl, d-C2alkoxy or halo-Cι-C2alkoxy; R8 is mono- to trisubstituted aryl, where the substituents are selected from the group consisting of halogen, d-C2alkyl, halo- d-C2alkyl, and halo-d-C2alkoxy, and can be identical or different if their number is greater than 1 ; X is O; and n is 1.
24. Compound of the formula (I) according to claim 1 , wherein Ri is aryl which is mono- to trisubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ; R2 is aryl which is unsubstituted or mono- to trisubstituted by R7, where the substituents can in each case be identical or different if their number is greater than 1 ; R3 is hydrogen; R4, R5 and R6 independently of one another are hydrogen or d- C2alkyl; R7 is halogen or halo-d-C2alkyl; R8 is mono- or disubstituted aryl, where the substituents are selected from the group consisting of halogen and halo-d-C2alkyl, and can be identical or different if their number is greater than 1 ; X is O; and n is 1.
25. Compound of the formula (I) according to claim 1, named N-(1-cyano-1-[2,3- dichlorophenoxymethyl]ethyl)-C-phenylmethanesulphonamide.
26. Process for the preparation of compounds of the formula (I), in each case in free form or in salt form, according to Claim 1 , characterized in that a compound of the formula
Figure imgf000052_0001
which is known or can be prepared in analogy to corresponding known compounds and in which R1f R3, R , R5, R6, X and n are as defined for the formula (I), is reacted with a compound of the formula
Figure imgf000052_0002
which is known or can be prepared in analogy to corresponding known compounds and in which R2 are as defined for the formula (I) and Q is a leaving group, if appropriate in the presence of a basic catalyst, and in each case, if desired, a compound of the formula (1), in each case in free form or in salt form, obtainable according to the process or in another manner, is converted into another compound of the formula (1), a mixture of isomers obtainable according to the process is separated and the desired isomer is isolated and or a free compound of the formula (I) obtainable according to the process is converted into a salt or a salt of a compound of the formula (I) obtainable according to the process is converted into the free compound of the formula (I) or into another salt.
27. Composition for the control of parasites, which, in addition to carriers and/or dispersants, contains as active compound at least one compound of the formula (I) according to Claim 1.
28. Use of compounds of the formula (I) according to Claim 1 for the control of parasites.
29. Process for the control of parasites, characterized in that an efficacious amount of at least one compound of the formula (I) according to Claim 1 is employed against the parasites.
30. Use of a compound of the formula (I) according to Claim 1 in a process for the control of parasites in warm-blooded animals.
31. Use of a compound of the formula (I) according to Claim 1 for the production of a pharmaceutical composition against parasites in warm-blooded animals.
PCT/EP2003/006483 2002-06-19 2003-06-18 N-sulphonylaminoacetonitriles having pesticidal properties WO2004000798A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BR0311967-0A BR0311967A (en) 2002-06-19 2003-06-18 N-sulfonylaminoacetonitriles having pesticidal properties
AU2003242735A AU2003242735B8 (en) 2002-06-19 2003-06-18 N-sulphonylaminoacetonitriles having pesticidal properties
EP03760656A EP1517887A1 (en) 2002-06-19 2003-06-18 N-sulphonylaminoacetonitriles having pesticidal properties
US10/518,063 US20050222448A1 (en) 2002-06-19 2003-06-18 N-sulphonylaminoacetonitriles having pesticidal properties
KR10-2004-7020580A KR20050014011A (en) 2002-06-19 2003-06-18 N-Sulphonylaminoacetonitriles Having Pesticidal Properties
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JP2004514794A JP2005529967A (en) 2002-06-19 2003-06-18 N-sulfonylaminoacetonitrile having pest control properties
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US7964621B2 (en) 2008-10-21 2011-06-21 Merial Limited Thioamide compounds, method of making and method of using thereof
EP2471363A1 (en) 2010-12-30 2012-07-04 Bayer CropScience AG Use of aryl-, heteroaryl- and benzylsulfonamide carboxylic acids, -carboxylic acid esters, -carboxylic acid amides and -carbonitriles and/or its salts for increasing stress tolerance in plants
US8461176B2 (en) 2008-11-14 2013-06-11 Merial Limited Enantiomerically enriched aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof
EP2957557A1 (en) * 2014-06-17 2015-12-23 Novartis Tiergesundheit AG New compounds
WO2018108627A1 (en) 2016-12-12 2018-06-21 Bayer Cropscience Aktiengesellschaft Use of substituted indolinylmethyl sulfonamides, or the salts thereof for increasing the stress tolerance of plants
US10065926B2 (en) 2013-10-04 2018-09-04 Bayer Cropscience Aktiengesellschaft Use of substituted dihydrooxindolylsulfonamides, or the salts thereof, for increasing the stress tolerance of plants
WO2019025153A1 (en) 2017-07-31 2019-02-07 Bayer Cropscience Aktiengesellschaft Use of substituted n-sulfonyl-n'-aryl diaminoalkanes and n-sulfonyl-n'-heteroaryl diaminoalkanes or salts thereof for increasing the stress tolerance in plants
WO2022268520A1 (en) 2021-06-21 2022-12-29 Bayer Aktiengesellschaft Use of substituted pyrrolidinones or their salts for increasing stress tolerance of plants

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EP2350212A4 (en) * 2008-11-07 2012-05-23 Huntsman Petrochemical Llc Polyaminoacetonitriles, their methods of preparation and use
US8822689B2 (en) 2012-09-19 2014-09-02 Merial Limited Aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof

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EP1660441A2 (en) * 2003-08-29 2006-05-31 Syngenta Participations AG N-sulfonyl-alpha-amino-acid derivatives
US8314146B2 (en) 2008-10-21 2012-11-20 Merial Limited Thioamide compounds, method of making and method of using thereof
US7964621B2 (en) 2008-10-21 2011-06-21 Merial Limited Thioamide compounds, method of making and method of using thereof
US8461176B2 (en) 2008-11-14 2013-06-11 Merial Limited Enantiomerically enriched aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof
WO2012089722A2 (en) 2010-12-30 2012-07-05 Bayer Cropscience Ag Use of open-chain carboxylic acids, carbonic esters, carboxamides and carbonitriles of aryl, heteroaryl and benzylsulfonamide or the salts thereof for improving the stress tolerance in plants
WO2012089721A1 (en) 2010-12-30 2012-07-05 Bayer Cropscience Ag Use of substituted spirocyclic sulfonamidocarboxylic acids, carboxylic esters thereof, carboxamides thereof and carbonitriles thereof or salts thereof for enhancement of stress tolerance in plants
EP2471363A1 (en) 2010-12-30 2012-07-04 Bayer CropScience AG Use of aryl-, heteroaryl- and benzylsulfonamide carboxylic acids, -carboxylic acid esters, -carboxylic acid amides and -carbonitriles and/or its salts for increasing stress tolerance in plants
US10065926B2 (en) 2013-10-04 2018-09-04 Bayer Cropscience Aktiengesellschaft Use of substituted dihydrooxindolylsulfonamides, or the salts thereof, for increasing the stress tolerance of plants
EP2957557A1 (en) * 2014-06-17 2015-12-23 Novartis Tiergesundheit AG New compounds
WO2015195423A1 (en) * 2014-06-17 2015-12-23 Novartis Tiergesundheit Ag New sulfonylaminobenzamide compounds
US9714219B2 (en) 2014-06-17 2017-07-25 Novartis Tiergesundheit Ag Sulfonylaminobenzamide compounds
EA030490B1 (en) * 2014-06-17 2018-08-31 Эланко Тиргезундхайт Аг Sulfonylaminobenzamide compounds
WO2018108627A1 (en) 2016-12-12 2018-06-21 Bayer Cropscience Aktiengesellschaft Use of substituted indolinylmethyl sulfonamides, or the salts thereof for increasing the stress tolerance of plants
WO2019025153A1 (en) 2017-07-31 2019-02-07 Bayer Cropscience Aktiengesellschaft Use of substituted n-sulfonyl-n'-aryl diaminoalkanes and n-sulfonyl-n'-heteroaryl diaminoalkanes or salts thereof for increasing the stress tolerance in plants
WO2022268520A1 (en) 2021-06-21 2022-12-29 Bayer Aktiengesellschaft Use of substituted pyrrolidinones or their salts for increasing stress tolerance of plants

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JP2009007372A (en) 2009-01-15
CN1662489A (en) 2005-08-31
EP1517887A1 (en) 2005-03-30
NZ537039A (en) 2007-01-26
BR0311967A (en) 2005-03-29
KR20050014011A (en) 2005-02-05
CA2490123A1 (en) 2003-12-31
RU2005101203A (en) 2005-10-27
ZA200409580B (en) 2006-06-28
MXPA04012755A (en) 2005-03-23
AU2003242735A1 (en) 2004-01-06
JP2005529967A (en) 2005-10-06

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